KR101309368B1 - Resin composition for manufacturing thermoplastic polyester resin by using green catalyst - Google Patents

Abstract

The present invention relates to a composition for producing a polyester resin, wherein the molar ratio of the diol compound to dicarboxylic acid compound is a composition of 1.05 ~ 1.4, the composition is based on the weight of phosphorus compound 5 ~ 50ppm (P element amount), cobalt Disclosed is a composition for producing a polyester resin comprising a compound 10 ~ 40ppm (based on Co elemental amount), 0.2 ~ 20ppm color improving agent and 5-25 / 3 ~ 30ppm (based on Ti / Ge elemental) of titanium-germanium composite catalyst compound, In the production of polyester resins such as container molding using the same, it is harmless to the human body, environmentally friendly, and has an intrinsic viscosity higher than that of the conventional titanium catalyst compound, thereby improving the reaction rate during solid phase polymerization and reducing acetaldehyde generation due to thermal decomposition. It is effective in providing a composition for preparing a polyester resin that can be made, and titanium- By applying reuma titanium complex catalyst compound economical, it has the effect to maintain the improved color coordinate value than when using a conventional titanium catalyst compounds offer the yellowing improved polyester resin.

Description

Composition for manufacturing thermoplastic polyester resin using eco-friendly catalyst {RESIN COMPOSITION FOR MANUFACTURING THERMOPLASTIC POLYESTER RESIN BY USING GREEN CATALYST}

The present invention relates to a composition for producing a polyester resin, and more particularly to a composition for producing a polyester resin having a high viscosity (high I.V) excellent in transparency and color and suitable for use in container molding.

Polyester resin is one of the most commonly used resins, such as containers, sheets, films, fibers, injection products (injection products), the antimony oxide or antimony triacetate is most used as a catalyst in the production.

The antimony catalyst has the advantage of high productivity due to its excellent color and high activity during esterification (ES) and polycondensation (PC) reactions, but antimony is regulated as a harmful substance to the human body due to its toxicity and is therefore used worldwide. Therefore, the development of a new catalyst that is safe for the human body and environmentally friendly is required. In Japan, as an alternative to this problem, germanium catalysts have been used to produce polyester resins, but the cost of germanium catalysts is tens of times higher than that of antimony catalysts. This has been amplified.

As an alternative to these antimony catalysts, catalysts of titanium compounds have been developed. However, polyester resins prepared from the titanium catalysts disclosed are not suitable for container molding due to yellowish phenomena, and in solid state polymerization reactions. As the reaction rate is slowed, productivity is not only lowered. In addition, the pyrolysis rate is high in the process of making molded products such as containers, sheets, films, and fibers, and a lot of acetaldehyde is generated. There is a problem with limitations.

As a method for solving the problem with the titanium catalyst, US Patent No. 6,143,837 is a method for producing a polyester using a titanium compound catalyst, titanium alkoxide, acetyl acetonate, dioxide, titanate, and phosphite In order to improve the intrinsic viscosity (IV) during solid phase polymerization, a method of using pyromethyl acid dianhydride has been proposed. However, information on branching agents is limited and polyethylene terephthalate (hereinafter referred to as PET) using a titanium catalyst compound is proposed. ) There is a problem that there is no solution for color improvement, which is the biggest problem in manufacturing.

In addition, U.S. Patent No. 5,744,571 uses alkyl titanate as a titanium catalyst compound and proposes many color improving agents for improving the production, but there is a problem of lowering b value among color values by using organic colorants, There are no suggestions for improving the rate and thermal stability of the polymerization.

In addition, U.S. Patent No. 4,217,440 proposes a variety of methods for preparing branched polyesters using polyfunctional agents, but prior to the production of titanium catalysts, the purpose is not clear and the method of color improvement and titanium There is a problem that there is no technology that can improve the reaction rate of the solid phase polymerization, which is a disadvantage of the catalyst.

In addition, U.S. Patent No. 7,199,210 adds a blue agent and a red agent as color toners to improve color values when producing PET using a titanium catalyst compound and improves the rate of solid phase polymerization. Although a method of using pyromellitic dianhydride (PMDA) is disclosed as a possible method, this method has a limitation as a fundamental color improving agent using organic color toner, and also improves the rate of solid phase polymerization. As a solution for this, there is a lack of multifunctional additives in terms of its diversity using only PMDA.

In addition, U.S. Patent Application Publication No. 2007/0155947 discloses a method for preparing a polyester to improve the yellowing problem, which is a characteristic of a titanium catalyst, using a titanium catalyst and a magnesium compound. The problem of slowing down the rate of solid phase polymerization and the rapid decomposition of the solid phase caused many problems of acetaldehyde.

Therefore, the present invention has been made to solve the above problems, by using an environmentally friendly catalyst rather than antimony metal, harmless to the human body, environmentally friendly, reaction rate during solid phase polymerization, acetaldehyde generation, intrinsic viscosity suitable for container molding, yellowing phenomenon It is to provide a composition for producing a polyester resin that can solve all problems such as.

In addition, in applying an eco-friendly catalyst, a simple combination of existing catalysts without additional research and development such as a catalyst of a new structure is to provide a polyester resin having the most excellent color and intrinsic viscosity when manufacturing a polyester resin using the same.

As one aspect for solving the above problems, the present invention is a composition in which the molar ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4, wherein the composition is 5 to 50 ppm (based on P element amount) of the phosphorus compound, Provided is a composition for preparing a polyester resin comprising 10 to 40 ppm of cobalt compound (based on Co elemental content), 0.2 to 20 ppm of color improving agent and 5 to 25/3 to 30 ppm (based on Ti / Ge elemental content) of titanium-germanium composite catalyst compound. .

In addition, the composition for producing a polyester resin provides a composition for producing a polyester resin, characterized in that it further comprises a branching agent 10 ~ 500ppm.

Further, the branching agent is trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, diphenylsulfontetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, penta At least one member selected from the group consisting of erythritol, tetrahydrofuran, tetracarboxylic dianhydride, hydroxy terephthalic acid, dihydroxybenzoic acid, 1,2,2'-ethanetricarboxylic acid, glycerol and trimethylolpropane Provided is a composition for producing a polyester resin.

In addition, the titanium-germanium composite catalyst compound provides a composition for producing a polyester resin, characterized in that the titanium precursor and germanium precursor mixture is dissolved in ethylene glycol.

In addition, the titanium precursor is a titanium dioxide (TiO ₂ ) and silicon dioxide (SiO ₂ ) composite oxide, the germanium precursor provides a composition for producing a polyester resin, characterized in that the germanium dioxide (GeO ₂ ).

Further, the dicarboxylic acid compound may be phthalic acid, terephthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4, 4'-diphenyl ether dicarboxylic acid, 4,4'- diphenyl ketone dicarboxylic acid, 4,4'- diphenoxy ethane dicarboxylic acid, 4,4'- diphenyl sulfone dicarboxylic acid It provides a composition for producing a polyester resin, characterized in that at least one selected from the group consisting of acid and 2,6-naphthalenedicarboxylic acid.

In addition, the dicarboxylic acid compound provides a composition for producing a polyester resin, characterized in that consisting of 90 to 100 mol% of the terephthalic acid and 0 to 10 mol% of the isophthalic acid.

In addition, the diol compound is one or more selected from the group consisting of monoethylene glycol, diethylene glycol, 1,3-propylenediol, 1,4-butylenediol, 1,4-cyclohexanedimethanol and neopentyl glycol Provided is a composition for producing a polyester resin.

In addition, the cobalt compound provides a composition for producing a polyester resin, characterized in that the cobalt acetate.

The phosphorus compound may be phosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl phosphate, ethyl phosphate, isopropyl phosphate, or butyl phosphate. It provides a composition for producing a polyester resin, characterized in that at least one selected from the group consisting of, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate and triethylene glycol acid phosphate.

In addition, the color improving agent provides a composition for producing a polyester resin, characterized in that the blue dye or a red dye.

As another aspect for solving the above problems, the present invention provides a polyester resin produced using the composition, the color coordinate L value is 80.0 or more, the color coordinate b value is 0.0 or less and the intrinsic viscosity (IV) is 0.74 ~ 0.9 dl / g to provide.

The composition for preparing a polyester resin according to the present invention, in the production of a polyester resin, such as container molding using the same, is harmless to the human body and environmentally friendly, higher intrinsic viscosity than when using a conventional titanium catalyst compound to improve the reaction rate during solid phase polymerization And it is effective to provide a composition for producing a polyester resin that can reduce the generation of acetaldehyde due to thermal decomposition.

In addition, by applying the titanium-germanium composite catalyst compound of the optimum composition in applying an eco-friendly catalyst, it is economical and the effect of providing a polyester resin with improved yellowing phenomenon by maintaining a color coordinate value improved than when using a conventional titanium catalyst compound There is.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims and their equivalents. It is to be understood that various equivalents and modifications may be substituted for those at the time of the present application.

The present invention is a composition in which the molar ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4, wherein the composition is 5 to 50 ppm of phosphorus compound (based on P element amount) and 10 to 40 ppm of cobalt compound (based on Co element amount) by weight ), 0.2 ~ 20ppm color improving agent and 5-25 / 3 ~ 30ppm titanium-germanium composite catalyst compound (based on the Ti / Ge elemental content) provides a composition for preparing a polyester resin, preferably 10 ~ 500ppm of a branching agent It further provides a composition for producing a polyester resin.

The present invention is a problem of the yellowing of the resin color caused by using a titanium catalyst compound in the production of conventional polyester resins, the problem of solid-phase polymerization rate, the problem of acetaldehyde generated at the same time with the poor color coordinates due to thermal decomposition during the production of molded products using the prepared polyester resin And the problem of lowering transparency is solved by presenting a combination and an optimal content of components further comprising a phosphorus compound, a cobalt compound, a color improving agent and a titanium-germanium complex catalyst compound, and further, a branching agent. Hereinafter, each component of the present invention will be described in detail.

The composition for producing a polyester resin according to the present invention comprises a dicarboxylic acid compound and a diol compound as main raw materials.

The dicarboxylic acid compound includes an aromatic molecule as a main component of the diacid compound, and in the present invention, without limitation, phthalic acid, terephthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenyl Rendioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylethredicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, 4,4 ' -Diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like can be used, preferably terephthalic acid and / or other dicarboxylic acid Mixtures of compounds can be used. When the mixture is used, the terephthalic acid content is preferably at least 90 mol%, more preferably at least 95 mol%, most preferably at least 99 mol% of the total dicarboxylic acid compound. The most preferred composition of the mixture is a mixture of terephthalic acid and isophthalic acid.

The diol compound may be used, but not limited to monoethylene glycol, diethylene glycol, 1,3-propylenediol, 1,4-butylenediol, 1,4-cyclohexanedimethanol, neopentyl glycol, and the like. Monoethylene glycol alone, a mixture of monoethylene glycol or diethylene glycol and / or other diol compounds may be used. When the mixture is used, the monoethylene glycol or diethylene glycol content is preferably at least 95 mol%, more preferably 98 mol% or more of the total diol compound. The most preferred composition of the mixture is monoethylene glycol or a mixture of diethylene glycol and neopentyl glycol.

In the present invention, the content ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4 on a molar ratio basis. At this time, in order to improve the color and intrinsic viscosity of the composition for preparing a polyester resin according to the present invention and to prevent degradation of physical properties of the prepolymer, the content ratio is preferably 1.1 to 1.3.

In the present invention, the phosphorus compound is used as a heat stabilizer for preventing physical and chemical property changes of the resin due to heat, and includes 5 to 50 ppm (based on P element amount) based on the total weight of the final polyester resin composition. Preferably 25 to 35ppm may be included. When the phosphorus compound content is less than 5ppm may be reduced thermal stability and yellowing may occur, if the phosphorus compound content exceeds 50ppm may be disadvantageous in terms of manufacturing cost and fume occurs during the polycondensation reaction rather than reaction It can work against you.

The phosphorus compound includes, but is not limited to, phosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl phosphate, ethyl phosphate, isopropyl phosphate, and butyl Acid phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, triethylene glycol phosphate and the like can be used, preferably phosphoric acid, triethyl phosphate, ethyl phosphate can be used, more preferably Triethylphosphate may be used.

In the present invention, the cobalt compound serves as a colorant for color improvement during the preparation of the polyester resin, and includes 10 to 40 ppm (based on the amount of Co elements) based on the total weight of the final polyester resin composition. Preferably 25 to 35ppm may be included. When the cobalt compound content is less than 5ppm, the color b value may be high (a kind of color promoter), and when it exceeds 40ppm, it may be disadvantageous in terms of manufacturing cost, and color L and color b may be dark. .

Although it does not restrict | limit as said cobalt compound, It is preferable to use cobalt acetate.

In the present invention, the color improving agent is used for color improvement, such as a container formed by using a polyester resin, and includes 0.2 to 20 ppm based on the total weight of the final polyester resin composition. Preferably 5 to 15ppm may be included. When the content of the color improver is less than 0.2 ppm, the color improving effect may be insignificant, and when the color improver exceeds 20 ppm, the color may be slightly darkened.

The color improving agent is not limited, but it is preferable to use a blue dye or a red dye.

The branching agent (branching agents) in the present invention serves to improve the physical properties of the resin produced during the solid phase polymerization, it may be included in the 10 ~ 500ppm based on the total weight of the polyester resin composition to be produced. Preferably 30 to 300ppm may be included, more preferably 50 to 150ppm may be included. When the amount of the branching agent is less than 10ppm may increase the intrinsic viscosity of the resin produced may be insignificant, when it exceeds 500ppm may be rather dark.

The branching agents include, but are not limited to, trimellitic acid (TMLA), trimellitic anhydride (TMA), pyromellitic acid (PMLA), pyromellitic dianhydride (PMDA), Benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarb Acid dianhydride, diphenylsulfontetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pentaerythritol, tetrahydrofuran, tetracarboxylic dianhydride, hydroxy terephthalic acid, dihydroxybenzoic acid, 1,2 , 2'-ethanetricarboxylic acid, glycerol, trimethylolpropane and the like can be used, preferably trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromellitic dianhydride, more preferably Is trimellitic anhydride Water or pyromellitic dianhydride may be used.

According to the present invention, the catalyst used in the preparation of the polyester resin manufacturing composition is a titanium-germanium composite catalyst compound unlike the conventional titanium catalyst compound.

On the other hand, the present invention uses a titanium-germanium composite catalyst compound in order to further improve the productivity degradation problem due to the yellowing phenomenon of the polymer and the increase in viscosity of the solid phase polymerization when the existing titanium catalyst compound alone in the composition for producing a polyester resin.

The titanium-germanium composite catalyst compound preferably uses a solution formed by dissolving a titanium precursor and a germanium precursor mixture in ethylene glycol. In this case, the mixing ratio of the titanium precursor and the germanium precursor is 5 to 25/3 to 30 ppm (based on Ti / Ge element amount) based on the total weight of the final polyester resin composition. The titanium precursor may be a titanium dioxide (TiO ₂ ) / silicon dioxide (SiO ₂ ) composite oxide, it is preferable to use germanium dioxide (GeO ₂ ) as the germanium precursor.

In the present invention, the titanium-germanium composite catalyst compound includes 5 to 25/3 to 30 ppm (based on Ti / Ge elements) based on the total weight of the final polyester resin composition. Preferably 5 ~ 15/10 ~ 20ppm may be included, more preferably 8 ~ 12/12 ~ 16ppm may be included. The content of the titanium-germanium composite catalyst compound is a result derived by grasping the range of improvement of the color and the intrinsic viscosity of the polyester resin prepared in particular a composition for producing a polyester resin according to the present invention. Specifically, when the titanium content is less than 5ppm and the germanium content is less than 3ppm, the reaction may not be slowed or slowed down. When the titanium content is more than 25ppm and the germanium content is more than 30ppm, the titanium and germanium catalysts may be high. Due to the activity, the color of the polymer may not be good.

The composition for preparing a polyester resin according to the present invention may further include an antioxidant, a sunscreen, an antistatic agent, a flame retardant, a surfactant, and the like, as necessary.

The polyester resin manufacturing method using the composition for producing a polyester resin according to the present invention may be based on a method commonly used in the art, and the method is not particularly limited. For example, it can be prepared by the following method using a batch reactor. Of course, it may be carried out continuously and is not particularly limited.

That is, the preparation of the polyester resin using the composition for producing a polyester resin according to the present invention comprises the steps of (A) mixing a quantified dicarboxylic acid compound and a diol compound to prepare a slurry; (B) adding a titanium-germanium composite catalyst compound and a branching agent to the slurry and then esterifying; (C) adding a phosphorus compound, a cobalt compound and a color improving agent after the esterification reaction to prepare a polymerized product; (D) condensation polymerization of the polymer; (E) manufacturing a molten chip by discharging the reactants formed by the polycondensation reaction; And (F) crystallizing the molten chip to perform solid phase polymerization.

Here, the titanium-germanium complex catalyst compound may be added between the step (A) or (B) and (C).

In addition, additives such as the phosphorus compound, the cobalt compound, and the color improving agent may be added in the step (A).

Another example of the polyester resin manufacturing method of the present invention will be described in more detail. First, additives such as catalysts are prepared by using a dicarboxylic acid and diol as a main component in a prepared stirrer to make a slurry, and then transferred to an esterification reactor. After the esterification reaction proceeds to at least 80% or more, preferably 90% or more, other additives such as a heat stabilizer are added to the condensation polymerization reactor to carry out condensation polymerization. Thereafter, the reaction is carried out in a condensation polymerization reaction up to a polymerization degree of 100 or more, followed by cutting in water to prepare a melt chip having an inherent viscosity of 0.5 to 0.7 dl / g. The cut molten chip may be transferred to a solid state polymerizer to prepare a polyester resin for forming a container having an intrinsic viscosity of 0.7 to 0.9 dl / g.

In addition, the esterification reaction is allowed to react under stirring at a temperature of 220 to 290 ° C., preferably 245 to 265 ° C., and a pressure of 0.1 to 5 kg / cm 2, preferably 0.5 to 3 kg / cm 2 for about 1 to 10 hours. Can be. At this time, it is preferable that the water generated during the esterification reaction be immediately removable.

The polycondensation reaction may be reacted under stirring at a temperature of 250 to 300 ° C., preferably 270 to 290 ° C., and a pressure of 0.1 to 5 torr, preferably 0.5 to 2 torr for 1 to 20 hours. At this time, it is preferable that the ethylene glycol and by-products generated by the polycondensation reaction can be removed immediately.

Like the above-described method, the catalyst compound, phosphorus compound, cobalt compound, color improving agent and branching agent may be added at any stage before the slurry preparation step, after the esterification reaction or before the condensation polymerization reaction. However, the branching agent is added to the slurry in the case of the acid compound, and in the case of the anhydride compound is preferably added after the esterification reaction or before the condensation polymerization step.

The solid phase polymerization reaction may be carried out under a temperature of 195 ~ 230 ℃, the pressure of 0.2 ~ 2torr or nitrogen atmosphere.

The polyester resin prepared according to the composition for preparing a polyester resin and the polyester resin manufacturing method according to the present invention has a color coordinate L value of 80.0 or more, a color coordinate b value of 0.0 or less and an intrinsic viscosity (IV) of 0.74 to 0.9㎗ / It exhibits physical properties of g and is particularly suitable for use in container forming. Here, the color coordinate L value indicates how bright the sample is as an index indicating the brightness of the resin, and the color coordinate b value indicates the yellowishness of the resin. The higher the L value, the brighter the b value, and the higher the b value, the yellowish the color.

Further, as the polyester resin, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polyester (PETG), polyethylene naphthalate (PEN), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), and the like, but are not limited thereto.

Hereinafter, the present invention will be described in detail through specific preparation examples, examples, and comparative examples.

Manufacturing example

The melt polymerizer used to prepare the polyester resin was a batch polymerizer, and the reactor includes one esterification reactor, one condensation polymerization reactor, and a reactor equipped with a cutting system, and the esterification reaction was 3 to 4 hours, The polycondensation reaction was carried out for 2 to 3 hours, and the polyester resin was prepared by increasing the temperature to 285 ° C. under reduced pressure such that the final vacuum degree was 1.0torr or less. In addition, the solid phase polymerization reactor used a batch reactor for solid phase polymerization for 10 hours at a reaction temperature of 225 ℃, pressure 0.4torr or less.

Example  One

As a main raw material, a diol compound consisting of 100 mol% of monoethylene glycol was added at a molar ratio of 1.2 to a dicarboxylic acid compound consisting of 97 mol% of terephthalic acid and 3 mol% of isophthalic acid. 30 ppm of compound (triethyl phosphate), 30 ppm of cobalt compound (cobalt acetate), 6.1 ppm of blue dye (Global PRT, Color Matrix), 4.0 ppm of red dye (Global PRT, Color Matrix) and titanium-germanium composite catalyst compound 10/14 ppm (prepared by dissolving titanium dioxide / silicon dioxide composite oxide (C-94, Zatleben Co., Germany) and germanium dioxide in ethylene glycol) were weighed into each of the slurry preparation steps to prepare a polyester resin.

Example  2

A polyester resin was prepared in the same manner as in Example 1, except that 100 ppm of a branching agent (pyromellitic dianhydride) was further added in Example 1.

Comparative example  One

A polyester resin was prepared in the same manner as in Example 1, except that 13 ppm of a titanium catalyst compound was added instead of the titanium-germanium composite catalyst compound, and a blue dye and a red dye were not added. Here, the titanium catalyst compound used a titanium chelate compound (chelate compound made of tetraisopropyl titanate and aminocarboxylic acid), which is known as a compound having the highest activity, is the same in the following comparative example.

Comparative example  2

A polyester resin was added in the same manner as in Example 1 except that 13 ppm of a titanium catalyst compound was added instead of the titanium-germanium composite catalyst compound, 0.7 ppm of a blue dye and 0.5 ppm of a red dye were added. Prepared.

Comparative example  3

Except that the titanium catalyst compound 13ppm in place of the titanium-germanium composite catalyst compound in Example 1, 1.2ppm blue dye, 0.7ppm red dye and 100ppm of branching agent (pyromellitic dianhydride) was added. A polyester resin was prepared in the same manner as in Example 1.

Comparative example  4

A polyester resin was prepared in the same manner as in Example 1, except that 13 ppm of a titanium catalyst compound was added instead of the titanium-germanium composite catalyst compound in Example 1.

Comparative example  5

A polyester resin was prepared in the same manner as in Example 1, except that 230 ppm of an antimony catalyst compound (antimony oxide) was added without adding a titanium-germanium composite catalyst compound, a blue agent dye, and a red agent dye in Example 1. Was prepared.

Comparative example  6

A polyester resin was added in the same manner as in Example 1, except that 13 ppm of a titanium catalyst compound was added instead of the titanium-germanium composite catalyst compound, and 1.2 ppm of a blue dye and 0.7 ppm of a red dye were added. Prepared.

Comparative example  7

Except that the titanium catalyst compound 13ppm was added in place of the titanium-germanium complex catalyst compound in Example 1, 1.2ppm of the blue dye, 0.7ppm of the red dye and 50ppm of the branching agent (pyromellitic dianhydride). A polyester resin was prepared in the same manner as in Example 1.

The additive content (unit: ppm) excluding the dicarboxylic acid compound and the diol compound in the polyester resin prepared according to the above Examples and Comparative Examples is summarized in Table 1 below.

Experimental Example

Intrinsic viscosity and color L, a, and b were measured for the molten chip and the solid chip manufactured according to the Examples and Comparative Examples, and the results of the physical properties and the evaluation of the process properties were summarized in Table 2 below. Process property evaluation was judged by combining the results of intrinsic viscosity and color properties.

Referring to Table 2, in the case where the titanium-germanium complex catalyst compound, the color improving agent, the phosphorus compound, and the cobalt compound are included (Example 1) and the branching agent is further included (Example 2), the inherent characteristics of the molten chip and the solid state chip are shown. It can be seen that the viscosity, color L and color b are all optimal compositions suitable for use in container molding. At this time, it can be seen that the intrinsic viscosity can be further improved by adding a branching agent.

On the contrary, in the case where the catalyst compound is composed of only the titanium catalyst compound corresponding to the catalyst compound of the embodiment and does not include other additives except the phosphorus compound and the cobalt compound (Comparative Example 1), the intrinsic viscosity of color L, color b and the solid state chip You can see that it falls. In addition, it can be seen that when the color improver of the same amount as the Example is added (Comparative Example 4), color L and color b is lower than the Example, when the branching agent is added (Comparative Examples 3 and 7) It can be seen that the intrinsic viscosity rises but also falls in comparison with the embodiment in terms of color. In addition, it can be seen that when the catalyst compound is composed of only the titanium catalyst compound corresponding to the catalyst compound of the example and the content of the color improver is somewhat low (Comparative Examples 2 and 6), the color b falls.

On the other hand, when the catalyst compound is composed of only the antimony catalyst compound (Comparative Example 5) shows excellent physical properties as a whole, as described above, it is not preferable in terms of environmentally friendly.

As described above, the polyester resin prepared by using the composition for preparing a polyester resin according to the present invention is applied to the titanium-germanium composite catalyst compound together with the titanium catalyst compound, excellent intrinsic viscosity compared to the case of using only the conventional titanium catalyst compound , color L and color b can be obtained, which is harmless to the human body and is environmentally friendly, further compensating for the yellowing problem of polyester chips and molded products, which is a disadvantage of the conventional titanium catalyst, and further slowing down the solid-state polymerization rate. It can be improved.

Claims (12)

A molar ratio of the diol compound to the dicarboxylic acid compound is a composition of 1.05 to 1.4, wherein the composition is 5 to 50 ppm of phosphorus compound (based on P element amount), 10 to 40 ppm of cobalt compound (based on Co element amount), color It is a composition for producing a polyester resin containing 0.2 to 20 ppm of an improving agent and 8 to 15/3 to 16 ppm (based on Ti / Ge elemental content) of the titanium-germanium composite catalyst compound,
Color coordinate L value of the polyester resin manufactured using the said composition is 80.0 or more, the color coordinate b value is 0.0 or less, and the intrinsic viscosity (IV) is 0.74-0.9 dl / g, The composition for polyester resin manufacture. The method of claim 1,
The polyester resin composition for producing a polyester resin composition further comprises a branching agent 10 ~ 500ppm. The method of claim 2,
The branching agent is trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,4,5,8 -Naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, diphenylsulfontetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pentaerythritol, Tetrahydrofuran, tetracarboxylic dianhydride, hydroxy terephthalic acid, dihydroxybenzoic acid, 1,2,2'-ethanetricarboxylic acid, glycerol and trimethylolpropane Polyester resin composition. The method of claim 1,
The titanium-germanium composite catalyst compound is a composition for producing a polyester resin, characterized in that the titanium precursor and germanium precursor mixture is dissolved in ethylene glycol. 5. The method of claim 4,
The titanium precursor is a titanium dioxide (TiO ₂ ) and silicon dioxide (SiO ₂ ) complex oxide, the germanium precursor is a composition for producing a polyester resin, characterized in that the germanium dioxide (GeO ₂ ). The method of claim 1,
The dicarboxylic acid compound is phthalic acid, terephthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4 ' -Diphenylethanedicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid and A composition for producing a polyester resin, characterized in that at least one member selected from the group consisting of 2,6-naphthalenedicarboxylic acid. The method according to claim 6,
The dicarboxylic acid compound is 90 to 100 mol% of the terephthalic acid and 0-10 mol% of the isophthalic acid composition for producing a polyester resin. The method of claim 1,
The diol compound is at least one member selected from the group consisting of monoethylene glycol, diethylene glycol, 1,3-propylenediol, 1,4-butylenediol, 1,4-cyclohexanedimethanol and neopentyl glycol The composition for polyester resin manufacture. The method of claim 1,
The cobalt compound is a composition for producing a polyester resin, characterized in that the cobalt acetate. The method of claim 1,
The phosphorus compound is phosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl phosphate, ethyl phosphate, isopropyl phosphate, butyl phosphate, dibutyl phosphate A composition for producing a polyester resin, characterized in that at least one member selected from the group consisting of ethyl phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate and triethylene glycol acid phosphate. The method of claim 1,
The color improving agent is a composition for producing a polyester resin, characterized in that the blue dye or red dye. delete